Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

• the present invention relates generally to water-soluble polyvinyl alcohol (PVOH) polymers and articles, especially films for packaging and for encapsulating particulate products.
• PVOH polyvinyl alcohol
• the cold water-soluble PVOH/Alkyl Acrylate copolymers of the invention have a substantially random distribution of monomers which is reflected in its cold water solubility and GPEC chromatograms.
• PVOH Polyvinyl alcohol
• BACKGROUND Polyvinyl alcohol is a synthetic resin generally prepared by the alcoholysis, usually termed hydrolysis or saponification, of polyvinyl acetate.
• Fully hydrolyzed PVOH where virtually all the acetate groups have been converted to alcohol groups, is a strongly hydrogen-bonded, highly crystalline polymer which dissolves only in hot water— greater than about 140° F (60° C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, the PVOH polymer then is known as partially hydrolyzed, it is more weakly hydrogen-bonded and less crystalline and is soluble in cold water— less than about 50° F. (1 0° C). Both fully and partially hydrolyzed PVOH types are commonly referred to as PVOH homopolymers although the partially hydrolyzed type is technically a vinyl alcohol-vinyl acetate copolymer.
• PVOH copolymer is generally used to describe polymers that are derived by the hydrolysis of a copolymer of a vinyl ester, typically vinyl acetate, and another monomer such as, for example, an ethylenically unsaturated monomer, e.g., 2-acrylamido-2-methyl propane sulfonic acid; see United States Patent Nos.: 7,932,328; 7,790,81 5; 7,786,229 and 6,81 8,709 all to Vicari. PVOH copolymers can be tailored to desired film characteristics by varying the kind and quantity of copolymerized monomers.
• copolymerization process preferably includes splitting the quantity of AA into two parts, copolymerizing the first part of AA with all the required vinyl acetate monomer (VAM) in a first reactor and adding only the remaining AA into a second reactor and polymerizing with the copolymer from the first reactor.
• VAM vinyl acetate monomer
• a PVOH which has substantially random distribution of the comonomer composition has vastly improved solubility in cold water.
• the products are particularly useful for films used in packaging and for encapsulating particulate or liquid products.
• Encapsulated products which may be provided include fertilizer or other agricultural products, pharmaceutical products, biomedical products and cosmetic products.
• the polymers of the invention exhibit characteristic cold water dissolution times of less than 3 minutes, typically less than 2 minutes and preferably exhibit a characteristic cold water dissolution time of 1 minute or less.
• cold water film disintegration times are generally less than 2 minutes, typically less than 1 minute and preferably 45 seconds or less.
• Characteristic cold water dissolution times and characteristic cold water film disintegration times are measured on a 76 micron film; however, it will be appreciated that these parameters are a property of the polymer from which the film is made.
• the polymers of the invention may be made into any suitable thickness for use as a packaging film having a thickness of generally from 1 0 to 400 microns, typically having a thickness of from 20 to 200 microns and preferably having a thickness of from 25 to 1 00 microns.
• the polymers of the invention are also used to encapsulate core products such as particulate solids, liquids and/or gels by way of solution coating, emulsion coating, melt application , spray coating, immersion coating, fluid bed coating, or application with supercritical C0 2 .
• the polymers of the invention are generally applied with a film thickness of from 0.01 to 30 microns, more typically of from 0.05 to 25 microns, still more typically 0.1 to 20 microns such as from 0.25 to 5 microns. Film thicknesses of from 1 to 3 microns are suitably employed for encapsulating many products.
• GPEC Gradient Polarity Elution Chromatograph
• Figure 1 is a GPEC trace of a polyvinyl alcohol-methyl acrylate copolymer obtained from a 70:30 split comonomer addition ratio of VAM and methyl acrylate (MA) according to the present invention, exhibiting excellent aqueous solubility.
• the eluting polymer composition has substantially close polarity (substantial randomness) within a two minute interval as shown by the substantially single peak, or in other terms, the GPEC chromatogram is a substantially monomodal, that is, exhibits a single polymer peak.
• Figure 2 is a GPEC trace of a polyvinyl alcohol-methyl acrylate copolymer obtained from a 50:50 split comonomer addition ratio of VAM and MA, exhibiting hazy aqueous solubility.
• the peak shows substantial randomness as in Fig. 1 but slight broadening of the composition as shown by the appearance of a second peak as part of the within the same time interval. Note that the two peaks are close in elution time and overlap substantially over more than 50% of their height from their baselines; we refer to this class of GPEC chromatogram as a close polarity GPEC chromatogram.
• Figure 3 is a GPEC trace of a polyvinyl alcohol-methyl acrylate copolymer obtained from a 1 00:0 split comonomer addition ratio of VAM and MA, with poor aqueous solubility. Discrete peaks start to appear showing the presence of polymer compositions with different polarities, in the case of Figure 3 there is seen a bimodal GPEC chromatogram.
• a cold-water soluble, substantially random copolymer of vinyl alcohol (“VOH”) and alkyl acrylate (“AA”) prepared by copolymerizing vinyl acetate monomer (“VAM”) and AA, which copolymer exhibits a characteristic cold water film dissolution time of less than 3 minutes.
• VH vinyl alcohol
• AA alkyl acrylate
• the copolymer comprises from 2 to 25 mol % AA; typically, the copolymer comprises from 3 to 1 0 mol % AA and in preferred cases the copolymer comprises from 4 to 8 mol % AA.
• the random copolymer also exhibits a characteristic cold water film dissolution time of less than 2 minutes in typical embodiments and preferably the copolymer exhibits a characteristic cold water film dissolution time of less than 1 minute or less. Likewise, the copolymer preferably exhibits a characteristic cold water film disintegration time of less than 1 minute and has a monomodal GPEC chromatogram, such as that shown in Figure 1 .
• the AA is suitably selected from methyl acrylate (MA), ethyl acrylate, methyl methacrylate, ethyl methacrylate and mixtures thereof, especially either methyl acrylate or ethyl acrylate.
• MA methyl acrylate
• ethyl acrylate ethyl acrylate
• methacrylate methyl methacrylate
• ethyl methacrylate ethyl methacrylate
• mixtures thereof especially either methyl acrylate or ethyl acrylate.
• a packaging film made from the copolymer generally has a thickness of from 1 0 microns to 400 microns, suitably from 25 microns to 1 00 microns.
• the invention provides an encapsulated product comprising an outer encapsulation film surrounding a core product, wherein the encapsulating film comprises a cold water soluble, substantially random copolymer of vinyl alcohol (“VOH”) and alkyl acrylate (“AA”) prepared by copolymerizing vinyl acetate monomer (“VAM”) and AA, which copolymer exhibits a characteristic cold water film dissolution time of less than 3 minutes.
• VH vinyl alcohol
• AA alkyl acrylate
• VAM vinyl acetate monomer
• the encapsulating film generally has a thickness of from 0.05 microns to 25 microns, typically from 0.25 microns to 5 microns and encapsulates a particulate solid.
• the invention also includes a continuous process for making copolymers of vinyl acetate and methyl acrylate.
• VAM and methyl acrylate may be, for example, 2-ethylhexyl peroxydicarbonate (Trigonox EHP), 2,2'-azobisisobutyronitrile (AIBN), t-butyl peroxyneodecanoate, bis(4-t-butylcyclohexyl)
• peroxydicarbonate any initiator able to generate free radicals can be used.
• a solvent for the comonomers VAM and MA, the polymerization initiator and the copolymer being formed in the two reaction zones is generally employed in the process.
• Suitable solvents are, for example, methanol, ethanol, and propanol.
• the preferred solvent is methanol.
• the total amount of required MA continuously fed to both reaction zones is split into two parts: a first part for the first reaction zone, and the remaining quantity (the second part) for the second reaction zone.
• the "split" or ratio between the amounts of MA fed to the first reaction zone (first part) and the second reaction zone (second part), respectively, may be, for example, from about 50:50 to about 80 :20, preferably from about 60:40 to about 75:25.
• the amount of polymerization initiator fed to the first reaction zone may be, for example, about 0.0001 to about 1 wt. % based on the weight of VAM being fed.
• the amount of solvent fed to the first reaction zone may be, for example, about 1 0 to about 40 wt. % based on the weight of VAM being fed.
• the polymerization initiator is preferably fed to the first reaction zone as a solution in the solvent at a concentration in the solvent of about 0.1 to about 1 0 wt. % based on the weight of the solution.
• the average residence time in the first reaction zone of the components fed to the first reaction zone may be, for example, in the range of about 30 to about 120 minutes, preferably about 45 to about 70 minutes.
• the reaction temperature in the first reaction zone is, for example, about 55 to about 85°C preferably about 60 to about 80°C.
• components in the effluent from the first reaction one and the additional MA fed to the second reaction zone may be, for example, in the range of about 30 to about 120 minutes, preferably about 45 to about 70 minutes.
• the reaction temperature in the second reaction zone may be, for example, about 55 to about 85°C, preferably about 60 to about 80°C.
• the pressure in each reaction zone may be in the range, for example, of about 1 to about 30 psig, preferably about 3 to about 1 5 psig.
• the residence times and temperatures in the first and second reaction zones are generally sufficient to result in the polymerization of
• the polymer solids content in the effluent from the second reaction zone may be, for example, in the range of about 30 to about 85%, preferably about 55 to about 75%, while the percent conversion calculated from actual polymer solids content and the theoretical polymer solids content equal to the amount of monomers added may be in the range of about 40 to about 99%, preferably about 45 to about 50 %.
• the molecular weight of the copolymer from the second reaction zone indicated by the viscosity of a 1 5 wt. % solution in methanol is in the range, for example, of about 20 to about 200 cps preferably about 35 to about 70 cps.
• the effluent from the second reaction zone may, for example, be fed to a stripping column to remove the more volatile components such as unreacted VAM from the copolymer of VAM and MA.
• the resulting "paste" is then mixed with an aqueous solution of a strong base such as sodium hydroxide, e.g., containing about 1 0 to about 50 wt. % of sodium hydroxide to provide base at a caustic mole ratio (CMR, ratio of moles of base to moles of acetate in the copolymer) of about 0.01 to about 0.1 .
• a strong base such as sodium hydroxide, e.g., containing about 1 0 to about 50 wt. % of sodium hydroxide to provide base at a caustic mole ratio (CMR, ratio of moles of base to moles of acetate in the copolymer) of about 0.01 to about 0.1 .
• an amount of a volatile alcohol e.g., methanol, may be also added to reduce the solids content in the paste to about 30 to about 65 wt. %.
• the resulting mass is then allowed to react at a temperature from about room temperature (RT, about 22°C), to about 50°C for a period, e.g., about 5 minutes to about 24 hours to obtain a percent hydrolysis of the acetate groups in the copolymer to hydroxyl groups, e.g., in the range of about 70 to about 99+%, preferably in the range of about 80 to about 95%.
• the saponified copolymer of VOH and MA may have, for example, about 1 to about 8 mol % of polymerized MA (poly MA), about 0 to about 4 mol % of polymerized VAM (PVAc) and about 75 to about 98 mol % of polymerized vinyl alcohol (PVOH), preferably about 2 to about 7 mol % of poly MA, about 0 to about 2mol % of PVAc, and about 90 to about 95 mol % of PVOH, a degree of hydrolysis of, for example, about 70 to about 99+%, preferably about 80 to about 95% indicated by C 13 NMR and a relative molecular weight indicated by the viscosity of a 4% aqueous- solution of the VOH copolymer of, for example, about 5 to about 30 cps, preferably about 1 5 to about 28 cps.
• Examples 1 -1 0 describe the preparation of copolymers of VAM and methyl acrylate by a continuous process under varying process conditions.
• Reactor 1 was fed continuously with vinyl acetate (VAM), methanol containing di(2-ethylhexyl) peroxydicarbonate (Trigonox EHP) initiator, and methyl acrylate, each as a separate feed line using metering pumps. To ensure accurate feed rates, each feed was placed on a balance and the feed rates checked by measuring the weight difference with time. Methyl acrylate was also fed continuously to the second reactor to minimize compositional drift (the split between Reactor 1 (PK1 ) and Reactor 2 (PK2) was 70:30). Table 1 lists the feed rates and initiator concentrations for the runs.
• Reactor 1 temperature was 60°C and Reactor 2 temperature was 64°C.
• the residence time was 96 minutes in each reactor.
• the polymer solution coming out of Reactor 2 was fed into an Oldershaw ® column to remove residual vinyl acetate using methanol vapors. Each run was 12 hours long to ensure the polymerization was lined-out.
• Table 2 shows the results from the polymerization of methyl acrylate with vinyl acetate in the examples, including relative molecular weight of the polymer indicated by the viscosity of a 1 5% solution in methanol, the actual percentage of solids in Reactor 2 and the percent conversions (figures in parentheses) calculated from the actual percent solids and theoretical percent solids (figures not in parentheses).
• Table 2 shows the overall conversion of vinyl acetate and methyl acrylate into polymer. Based on these theoretical solids levels, which are directly related to the conversion of monomers to copolymer, the conversions ranged from 45.93-58.23%. Residual methyl acrylate (50 ppm to 1 00 ppm) was determined by GC analysis.
• CMR Caustic mole ratio
• the 50% NaOH was diluted with enough MeOH when added to the paste to dilute the solids to 35%.
• the NaOH/MeOH was mixed into the paste by hand (1 0 to 20 min. of mixing) at room temperature.
• the paste was then allowed to react for the time and temperature shown in the above table. Saponification procedures similar to those described in Examples 1 -1 0 were carried out on the polymers of Examples 1 -1 0.
• Table 4 shows the compositions and properties of the saponified polymers for each of the examples of Tables 1 and 2 including mol percent of polymerized methyl acrylate, polymerized VAM (PVAc) and polymerized vinyl alcohol (PVOH), degree of hydrolysis indicated by C 13 NMR, relative molecular weight as indicated by the viscosity of a 4% solution in water and degree of hydrolysis indicated by titration.
• PVAc polymerized VAM
• PVOH polymerized vinyl alcohol
• C 13 NMR spectroscopy can be used to determine the copolymer composition and the randomness of the MA in the copolymer.
• the MA feed rate was the only variable to control the MA loading in the copolymer.
• GPEC is a technique which can be used to measure the chemical composition distribution in polymers by using mixtures of a solvent and non-solvent and is described in Cools et ai, "Determination of the Chemical Composition Distribution of
• Copolymers of Styrene and Butadiene by Gradient Polymer Elution Chromatography Journal of Chromatoqraph A, 736 (Elsevier Science B.V., 1996), pp. 125-130 , the disclosure of which is incorporated herein by reference.
• the copolymers of the invention the following conditions, materials and equipment were used:
• Mobile phase 1 ) start with 5% Acetonitrile, 95 % water;
• the polymer compositions shown in each of Figures 1 -3 show polarity peaks as the polymer elutes from the column. The closer the peaks are the less the compositional drift is in the composition of the copolymer.
• the 50:50 split ratio polymer in Fig. 2 shows that the composition of the polymer formed is becoming more uniform (less compositional drift) than the 1 00:0 split ratio addition, while the 70:30 split ratio addition polymer in Fig. 1 has a monomodal chromatogram which shows substantial absence of compositional drift.
• the invention includes a continuous process for making vinyl acetate/acrylate or acrylate derivative copolymers.
• Acrylate or acrylate derivative monomers and copolymers incorporating them are referred to herein as acrylate comonomers and acrylate copolymers, respectively, for purposes of convenience.
• a continuous process for making a vinyl acetate/acrylate copolymer comprising: (a) continuously supplying a reaction mixture including vinyl acetate and a more reactive acrylate comonomer to a reaction zone wherein the vinyl acetate and acrylate comonomer are at least partially consumed to form an intermediate reaction mixture; (b) continuously supplying to the intermediate reaction mixture a stream enriched with respect to the more reactive acrylate comonomer and copolymerizing the additional acrylate comonomer with the intermediate reaction mixture to form a vinyl acetate/acrylate copolymer product; and (c) continuously recovering the vinyl
• acetate/acrylate copolymer product Films were prepared from the PVOH made by the inventive process. In a typical experiment, water solutions of the copolymers were prepared (4-10 wt% solids) and cast onto glass plates. The solutions were allowed to dry overnight at room temperature, then peeled off the plates. The resulting films were conditioned at 22°C and 50% RH for at least 24 hours before the properties were measured. The properties of the thus-prepared film including the improved aqueous solubility are shown in Table 5.
• solubility characteristics of the films can be determined by the slide frame test described in United States Patent No. 7,745,51 7 which is incorporated herein in its entirety and is as follows. Films are prepared from the formulation by casting a 7% aqueous solution onto a glass plate, which is leveled by gravity and allowed to dry to a moisture content of from about 6 to 1 5% which may take from 2 to 7 days. An amount of the solution is added to the plate to provide for a film with a target thickness of about 76 ⁇ . A 2.3x3.4 cm sample of film is mounted in a slide frame and placed in a 500 ml beaker 30 filled with 400 ml water.
• the beaker is placed on a magnetic stirrer, and the water is stirred with a magnetic stir bar at 400 rpm set by a control knob, such that a vortex is created.
• the water temperature is maintained at 21 °C+/-1 °C.
• the frame is secured in the beaker with a clamp which is supported by a platform such that stirring water pushes against the film.
• the film begins to balloon or wave.
• the disintegration time is recorded when the film balloon bursts. After disintegration, the frame remains in water and the dissolution time is recorded as the total time (inclusive of disintegration time) when no residual strings of film and no film particles remain on the frame.
• the invention thus describes a process to prepare PVOH with improved aqueous solubility by feeding the MA comonomer in two parts in two reactors as opposed to all in the same reactor.
• attempts were made to make the copolymer by adding all the monomers and initiator into one reactor.
• Attempts to make the copolymer by adding all the required monomers in the first reactor itself only resulted in PVOH that were insoluble or significantly reduced solubility as shown in Table 6. This is believed to be due to the formation of methyl acrylate blocks and/or methyl acrylate homopolymers in the copolymer.
• Table 6 a film is deemed not to pass the dissolution test described above when it fails to disintigrate in three (3) minutes or more or it has a dissolution time of greater than ten (1 0) minutes.
• the invention also includes the following alternative embodiments:
• Alternative Embodiment No. 1 is a process for the production of a copolymer of vinyl alcohol (“VOH”) and alkyl acrylate (“AA”) (such as methyl acrylate (“MA”)) by copolymerizing vinyl acetate monomer (“VAM”) and AA, said process comprising:
• Alternative Embodiment No. 2 is a process of Alternative Embodiment No. 1 , wherein 1 00% of the required VAM is fed in step (a).
• Alternative Embodiment No. 3 is a process according to any of the preceding embodiments, wherein at least 80% of the required VAM is fed in step (a).
• Alternative Embodiment No. 4 is a process according to any of the preceding embodiments, wherein at least 90% of the required VAM is fed in step (a).
• Alternative Embodiment No. 5 is a process according to any of the preceding embodiments, wherein said solvent is methanol, ethanol or propanol.
• Alternative Embodiment No. 6 is a process according to any of the preceding embodiments, wherein said solvent is methanol.
• Alternative Embodiment No. 7 is a process according to any of the preceding embodiments, wherein the first part of MA and second part of MA are respectively in the ratio range of about 50:50 to about 80 :20.
• Alternative Embodiment No. 8 is a process according to any of the preceding embodiments, wherein the first part of MA and second part of MA are respectively in the ratio range of about 60:40 to about 75:25.
• Alternative Embodiment No. 9 is a process according to any of the preceding embodiments, wherein the amount of said solvent fed to the first reaction zone is about 1 0 to about 40 wt. % based on the weight of VAM being fed.
• Alternative Embodiment No. 1 0 is a process according to any of the preceding embodiments, wherein the average residence time in the first and second reaction zones of the components fed to the said reaction zones is about 30 to about 120 minutes.
• Alternative Embodiment No. 1 1 is a process according to any of the preceding embodiments, wherein said average residence time is about 45 to about 70 minutes.
• Alternative Embodiment No. 12 is a process according to any of the preceding embodiments, wherein the reaction temperature in said first and second reaction zones is about 55 to about 85°C.
• Alternative Embodiment No. 13 is a process according to any of the preceding embodiments, wherein said reaction temperature is about 60 to 80°C.
• Alternative Embodiment No. 14 is a process according to any of the preceding embodiments, wherein the average reaction pressure in each reaction zone is about 1 to about 30 psig.
• Alternative Embodiment No. 1 5 is a process according to any of the preceding embodiments, wherein said reaction pressure is about 3 to about 1 5 psig.
• Alternative Embodiment No. 16 is a process according to any of the preceding embodiments, wherein the residence times and temperatures in the first and second reaction zone result in the polymerization of substantially all the MA fed to the system.
• Alternative Embodiment No. 17 is a process according to any of the preceding embodiments, wherein the effluent from said second reaction zone has an actual polymer solids content of about 35 to about 85% and the percent conversion calculated from said actual polymer solids content and the theoretical polymer solids content equal to the amount of monomers added to the system is about 45 to about 60 %.
• Alternative Embodiment No. 18 is a process according to any of the preceding embodiments, wherein the relative molecular weight of the VAM/MA copolymer obtained from the second reaction zone is indicated by a viscosity of a 1 5 wt. % solution of the copolymer in methanol of about 35 to about 80 cps.
• Alternative Embodiment No. 19 is a process according to any of the preceding embodiments, wherein said percent conversion is about 40 to about 60%.
• Alternative Embodiment No. 20 is a process according to any of the preceding embodiments, wherein the saponified copolymer of VOH and MA contains about 1 to about 8 mol % of polymerized MA, about 85 to about 98 mol % of polymerized VOH (PVOH), a degree of hydrolysis of about 70 to at least 99% indicated by C 13 NMR and a relative molecular weight indicated by a viscosity of a 4% aqueous solution of the VOH copolymer of about 1 5 to about 30 cps.
• Alternative Embodiment No. 22 is a copolymer of vinyl acetate and an alkyl acrylate prepared by a process comprising:
• reaction mass wherein said first part of AA and said second part of MA together account for all the required quantity of AA.
• Embodiment No. 22 wherein the first part of MA and second part of MA are respectively in the ratio range of about 50:50 to about 80:20.
• Alternative Embodiment No. 24 is the copolymer of Alternative
• Embodiment No. 23 wherein the first part of MA and second part of MA are respectively in the ratio range of about 60:40 to about 75:25.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=45478541

Family Applications (1)

Country Status (6)

Cited By (13)

Families Citing this family (4)

Citations (8)

Family Cites Families (30)

• 2011
  • 2011-12-16 CN CN2011800680936A patent/CN103403043A/zh active Pending
  • 2011-12-16 US US13/328,338 patent/US10316124B2/en active Active
  • 2011-12-16 JP JP2013546257A patent/JP5931088B2/ja active Active
  • 2011-12-16 ES ES11808485.4T patent/ES2543044T3/es active Active
  • 2011-12-16 WO PCT/US2011/065473 patent/WO2012087821A1/en active Application Filing
  • 2011-12-16 EP EP11808485.4A patent/EP2655447B1/de not_active Revoked
• 2015
  • 2015-11-04 JP JP2015216584A patent/JP6117893B2/ja active Active
• 2017
  • 2017-03-22 JP JP2017055585A patent/JP6454745B2/ja active Active

Patent Citations (10)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events